强酸性离子交换树脂催化合成乙酸正丁酯动力学Kinetics of Catalytic Synthesis of n-butyl Acetate Using Strong Acid Ion Exchange Resin as Catalyst
廖安平,左卫元,蓝平,蓝丽红,李媚,童张法
摘要(Abstract)：
为了获得D072型强酸性离子交换树脂催化剂合成乙酸正丁酯反应动力学方程,在间歇釜式反应器中,消除内外扩散后,测定不同反应条件下乙酸浓度随时间的变化,反应体系按拟均相处理,用初始速率法回归估算动力学模型参数。在催化剂平均粒度小于0.074 mm,搅拌速度大于150 r min 1时,可基本消除内外扩散的影响。在常压,催化剂用量为0.01665～0.08333 gcat gA 1,温度为326.2~358.2 K的条件范围,获得的动力学模型参数为:k0=8.86×104L mol 1 min 1 gcat 1,Ea=60728.86 J mol 1,平衡常数受温度的影响不大。在实验条件范围对获得的动力学方程进行了验证,最大相对偏差小于8.3%%,计算值与实验值符合较好。
关键词(KeyWords)： 强酸性离子交换树脂;乙酸正丁酯;合成;反应动力学
基金项目(Foundation): 国家自然科学基金项目(21066002);; 广西科学研究与技术开发计划项目(桂科能0992028-13);; 广西高校人才小高地项目(桂教人20114712)
作者(Author): 廖安平,左卫元,蓝平,蓝丽红,李媚,童张法
参考文献(References)：
- [1]HAN Chun-yu(韩春玉),LIU Chun-sheng(刘春生),ZHANG Shao-hua(张少华).Catalytic synthesis of n-butyl acetate by chitosandoped with iron(Ⅲ)((壳聚糖负载铁(Ⅲ)催化合成乙酸正丁酯))[J].Contemporary Chemical Industry(当代化工),2011,40((3)):232-234:254.
- [2]Harmsen G J.Reactive distillation:The front-runner of industrial process intensification.A full review of commercial applications,research,scale-up,design and operation[J].Chemical Engineering and Processing.2007,46(9):774-780.
- [3]CUI Bo(崔波),GAO Peng,((高鹏)),JIN Qing((金青)).Characterization of solid super acid catalyst modified by La oxide andits catalysis on synthesis of ethgl acetate(镧改性固体超强酸催化剂表征及对乙酸乙酯合成的催化作用)[J].J Chem Eng ofChinese Univ(高校化学工程学报),2008,22(1):60-64.
- [4]von Erik H,Markus S,Sandra P,et al.Study of heterogeneously catalysed reactive distillation using the D+R tray—A novel type oflaboratory equipment[J].Chemical Engineering Research and Design,2011,89(8):1271-1280.
- [5]CAI Hong(蔡红),ZHOU Bin(周斌).Progress of ion exchange resins in organic catalysis(离子交换树脂在有机催化反应中的应用进展)[J].Chemical Industry and Engineering Progress(化工进展)2007,26(3):386-391.
- [6]HUO Wen-zhou(霍稳周),LI Hua-yi(李花伊),CHEN Ming(陈明).Synthesis of n-butyl acetate on thermal-stable cation exchangeresin catalyst(耐温强酸性阳离子交换树脂催化合成乙酸丁酯)[J].Petrochemical Technology(石油化工),2006,35(7):681-684.
- [7]QIU Ting(邱挺),HUANG Zhi-xian(黄智贤),CHENG Chun-biao(程春飚),et al.Synthesis of n-butyl acetate by catalyticdistillation(催化精馏合成乙酸丁醋的工艺研究)[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2008,24(6):545-550.
- [8]LIAO An-ping(廖安平),LAN Ping(蓝平),LiI Mei(李媚),et al.Synthesis of acetic ether using fluidizing catalytic reactionrectification(流化催化精馏制备乙酸乙酯研究)[J].Chemical Engineering(China)(化学工程),2000,28(6):19-21.
- [9]Shaojun M,Brent H S.Mechanism of acetic acid esterification over sulfonic acid-functionalized mesoporous silica[J].Journal ofCatalysis,2011,279(1):36-143.
- [10]Gangadwala J,Kienle A.MINLP optimization of butyl acetate synthesis[J].Chemical Engineering and Processing,2007,46(2):107-118.
- [11]LAN Li-hong(蓝丽红),YAN Rui-yi(闫瑞一),LI Mei(李媚),et al.Study on kinetics of catalytic synthesis of n-butyl acetate usingcationic membrane catalyst(阳离子交换膜催化合成乙酸丁酯动力学研究)[J].Ion Exchange and Adsorption(离子交换与吸附),2006,22((2)):168-174.
- [12]In Bum Ju,Hye-Won Lim,Wonjin Jeon,et al.Kinetic study of catalytic esterification of butyric acid and n-butanol over Dowex50Wx8-400[J].Chemical Engineering Journal,2011,168(1):293-302.
- [13]WU Zhi-nan(吴指南).Basic Organic Chemical Technology(基本有机化工工艺学)[M].Beijing(北京):Chemical Industry Press(化学工业出版社),1990,35.